Method for producing (z)-1-chloro-2,3,3-trifluoro-1-propene

ABSTRACT

Provided is a method for producing (Z)-1-chloro-2,3,3-trifluoro-1-propene where (E)-1-chloro-2,3,3-trifluoro-1-propene and water can be efficiently removed and (Z)-1-chloro-2,3,3-trifluoro-1-propene with higher purity can be obtained at a higher recovery ratio. The method for producing (Z)-1-chloro-2,3,3-trifluoro-1-propene includes: distilling a distillation composition which contains (Z)-1-chloro-2,3,3-trifluoro-1-propene, (E)-1-chloro-2,3,3-trifluoro-1-propene and water to remove (E)-1-chloro-2,3,3-trifluoro-1-propene and water as an azeotropic composition or an azeotropic-like composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/422,406, filed on May 24, 2019, which is a continuation of priorInternational Application No. PCT/JP2017/042462 filed on Nov. 27, 2017,which is based upon and claims the benefit of priority from JapanesePatent Application No. 2016-229919 filed on Nov. 28, 2016; the entirecontents of all of which are incorporated herein by reference.

FIELD

The present invention relates to a method for producing(Z)-1-chloro-2,3,3-trifluoro-1-propene.

BACKGROUND

It is planned that production of hydrochlorofluorocarbon (HCFC) isregulated due to its adverse effect on the ozone layer. Examples of HCFCinclude 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca),1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb), and so on.Development of a compound alternative thereto is demanded in accordancewith the regulation of HCFC.

An example of the compound alternative to HCFC includes, for example,1-chloro-2,3,3-trifluoropropene (HCFO-1233yd). HCFO-1233yd has a smallglobal warming potential (GWP) and can be suitably used for uses in acleaning agent, a solvent, a refrigerant, a foaming agent, aerosol, andso on.

There are a Z-isomer of HCFO-1233yd (HCFO-1233yd(Z)) and an E-isomer ofHCFO-1233yd (HCFO-1233yd(E)) being structural isomers in HCFO-1233yd.HCFO-1233yd(Z) is mainly used for the uses in the cleaning agent, thesolvent, the refrigerant, the foaming agent, and the aerosol.

International Publication No. 1994/14737 discloses a method forproducing 1,1,2,2,3-pentafluoropropane (HCFC-245ca) from1-chloro-2,2,3,3-tetrafluoropropane (HCFC-244ca) and hydrogen fluoride.Since HCFO-1233yd is secondary produced through this method, acomposition containing HCFO-1233yd is obtained by separating HCFO-1233ydfrom a composition obtained by the above-stated method.

Though HCFO-1233yd generated by the above method is a mixture ofHCFO-1233yd(E) and HCFO-1233yd(Z), it is preferable that each ofHCFO-1233yd(Z) and HCFO-1233yd(E) can be used independently, and acomposition of the mixture is adjustable depending on uses. However,International Publication No. 1994/14737 does not describe separation ofHCFO-1233yd(E) and HCFO-1233yd(Z), and adjustment of the composition.

There is a case when water is mixed in during a production process ofHCFO-1233yd. When water (moisture) is contained in the compositioncontaining HCFO-1233yd(Z), reliability and performance may deterioratewhen it is used as the cleaning agent, the solvent, the refrigerant, thefoaming agent, or the aerosol to cause various problems. A content ofwater is preferably reduced as much as possible in order to avoid suchan unfavorable influence.

In general, a by-product is removed from a reaction product throughdistillation by using a boiling point difference therebetween, butboiling points are close to one another such that the boiling point ofHCFO-1233yd(Z) is about 54° C. and the boiling point of HCFO-1233yd(E)is about 48° C., It is therefore difficult to separate by means of anormal distillation column, and a method to more efficiently removeHCFO-1233yd(E) has been demanded.

Further, separation by means of distillation is difficult because amixture of HCFO-1233yd(Z) and water forms an azeotropic-likecomposition, and a method to efficiently remove water has been demanded.

SUMMARY

The present invention is made to solve the above-stated problems, and anobject thereof is to provide a method for producing HCFO-1233yd(Z) whereHCFO-1233yd(E) and water are efficiently removed from a compositioncontaining HCFO-1233yd(Z), HCFO-1233yd(E) and water, and a recoveryratio of HCFO-1233yd(Z) is high, and purity of HCFO-1233yd(Z) can beincreased.

The present invention provides a method for producing HCFO-1233yd(Z)having a composition described below.

[1] A method for producing HCFO-1233yd(Z) characterized in thatdistilling a distillation composition containing HCFO-1233yd(Z),HCFO-1233yd(E) and water to remove HCFO-1233yd(E) and water as anazeotropic composition or an azeotropic-like composition.

[2] The method for producing HCFO-1233yd(Z) according to [1], wherein acontent ratio of water with respect to a sum total of a content ofHCFO-1233yd(E) and a content of water is 0.001 to 5 mass % in thedistillation composition.

[3] The method for producing HCFO-1233yd(Z) according to [1] or [2],wherein the distillation composition is prepared by addingHCFO-1233yd(E) to a composition containing HCFO-1233yd(Z) and water.

[4] The method for producing HCFO-1233yd(Z) according to [1] or [2],wherein the distillation composition is prepared by adding water to acomposition containing HCFO-1233yd(Z) and HCFO-1233yd(E).

[5] The method for producing HCFO-1233yd(Z) according to any one of [1]to [4], wherein the distillation composition is prepared by using areaction composition containing HCFO-1233yd(Z) obtained by subjectingHCFC-244ca to a dehydrofluorination reaction.

[6] The method for producing HCFO-1233yd(Z) according to any one of [1]to [5], wherein the distillation is carried out by a distillation columnwhose column top temperature is set to 40 to 55° C.

According to the method for producing HCFO-1233yd(Z) of the presentinvention, HCFO-1233yd(E) and water can be efficiently removed from acomposition containing HCFO-1233yd(Z), HCFO-233yd(E) and water, arecovery ratio of HCFO-1233yd(Z) can be increased, and purity ofHCFO-1233yd(Z) can be increased.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a view illustrating an example of a distillation apparatusused for a production method according to an embodiment.

DETAILED DESCRIPTION

In this specification, 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd) isalso just called “1233yd”. Further, a Z-isomer of HCFO-1233yd being astructural isomer of HCFO-1233yd is also just called “1233yd(Z)”, and anE-isomer of HCFO-1233yd is also just called “1233yd(E)”.

In this specification, as for halogenated hydrocarbon, when anabbreviated name of a compound is given in a parenthesis after acompound name, the abbreviated name is used instead of the compound nameaccording to need. As for a compound having a double bond in a moleculeand having an E-isomer and a Z-isomer, the E-isomer and the Z-isomer arerespectively represented by (E) or (Z) given at the end of theabbreviated name of the compound name. The compound name without (E) or(Z) at the end represents that the compound is any of the (E) isomer,the (Z) isomer, or a mixture of the (E) isomer and the (Z) isomer.

Hereinafter, embodiments of the present invention are explained.

A method for producing 1233yd(Z) according to the present embodiment ischaracterized in that distilling a distillation composition containing1233yd(Z), 1233yd(E) and water to remove 1233yd(E) and water from thedistillation composition as an azeotropic composition or anazeotropic-like composition. Here, a part or all of the azeotropiccomposition or the azeotropic-like composition of 1233yd(E) and watermay be removed.

First, the azeotropic composition and the azeotropic-like compositionare explained.

In general, the azeotropic composition is defined as one where acomposition of a gas phase generated by gasification of a liquid phasebecomes the same as a composition of the liquid phase, or a compositionof a liquid phase generated by liquefaction of a gas phase becomes thesame as a composition of the gas phase in a mixture. The azeotropiccomposition can be suitably used for distillation and reflux because acomposition thereof does not change through evaporation andcondensation. The composition of the azeotropic composition changesdepending on pressure conditions.

Meanwhile, the azeotropic-like composition exhibits similar behavior asthe azeotropic composition. That is, in the azeotropic-like composition,a composition of a gas phase generated by gasification of a liquid phasebecomes almost the same as a composition of the liquid phase, or acomposition of a liquid phase generated by liquefaction of a gas phasebecomes almost the same as a composition of the gas phase. Theazeotropic-like composition can be suitably used for distillation andreflux as same as the azeotropic composition because a compositionthereof does not change through evaporation and condensation.

The present inventors found that 1233yd(E) and water formed anazeotropic composition or an azeotropic-like composition. Further, thepresent inventors found that the azeotropic composition or theazeotropic-like composition of 1233yd(E) and water was formed inpreference to an azeotropic composition or an azeotropic-likecomposition of 1233yd(Z) and water.

The azeotropic composition or the azeotropic-like composition of1233yd(E) and water has a lower boiling point compared to 1233yd(Z).That is, the boiling point of 1233yd(Z) is about 54° C., where theboiling point of the azeotropic composition or the azeotropic-likecomposition of 1233yd(E) and water is about 40 to 48° C. The boilingpoint is a boiling point under atmospheric pressure. The atmosphericpressure is 101.325 kPa.

Accordingly, it is possible to separate 1233yd(Z) from 1233yd(E) andwater by using the azeotropic composition or the azeotropic-likecomposition of 1233yd(E) and water. It is thereby possible toefficiently remove 1233yd(E) and water from the distillationcomposition, increase a recovery ratio of 1233yd(Z), and increase purityof 1233yd(Z).

The azeotropic composition of 1233yd(E) and water has a relativevolatility represented by the following expression (1) under atmosphericpressure to be 1.00, and the azeotropic-like composition of 1233yd(E)and water has a relative volatility represented by the followingexpression (1) to be in a range of 1.00-0.20. Almost the same effect asthe azeotropic composition can be obtained if the azeotropic-likecomposition has the relative volatility in the above-stated range.

Relative volatility=(mol % of water in gas phase/mol % of 1233yd(E) ingas phase)/(mol % of water in liquid phase/mol % of 1233yd(E) in liquidphase)  (1)

A composition range capable of obtaining a desired relative volatilitycan be found as described below. First, the composition of the mixtureof 1233yd(E) and water is gradually changed to measure the compositionsof the liquid phase and the gas phase by using a Karl Fischer moisturemeter and a gas chromatograph. The relative volatility is calculatedfrom the above-stated expression (1) by using the compositions of theliquid phase and the gas phase. A correlation between the compositionand the relative volatility can be thereby found. The composition toobtain the desired relative volatility can be found from thiscorrelation.

In each of the azeotropic composition and the azeotropic-likecomposition of 1233yd(E) and water, a content ratio of water withrespect to a sum total of a content of 1233yd(E) and a content of wateris preferably 0.001 to 5 mass %. The relative volatility is likely tofall within the range of 1.00±0.20 and the boiling point is likely to beabout 40 to 48° C. as long as the content ratio of water falls withinthe above-stated range. The ratio is more preferably 0.01 to 2.5 mass %,further preferably 0.05 to 2 mass %, and particularly preferably 0.1 to2 mass % in terms of making the relative volatility close to 1.00 andlowering the boiling point.

Next, a distillation composition is explained.

The distillation composition contains 1233yd(Z), 1233yd(E) and water.The distillation composition may be prepared by adding at least one kindselected from 1233yd(E) and water to a composition containing at leastone kind selected from 1233yd(E) and water, and 1233yd(Z) according toneed.

It is possible to obtain 1233yd through a method, for example, disclosedin International Publication No. 1994/14737. That is, 1233yd can beobtained as a by-product when 1,1,2,2,3-pentafluoropropane (HCFC-245ca)is produced by supplying 1-chloro-2,2,3,3-tetrafluoropropane(HCFC-244ca) and hydrogen fluoride in the presence of a chromiumhydroxide catalyst.

It is possible to obtain 1233yd by, for example, a dehydrofluorinationreaction of HCFC-244ca. The reaction can be carried out by using, forexample, potassium hydroxide, sodium hydroxide, and the like as areactant, at the temperature of 40 to 80° C.

1233yd obtained by these production methods is generally a mixture of1233yd(Z) and 1233yd(E), and there is a case when water is mixed induring a production process. That is, a reaction composition containingat least one kind selected from 1233yd(Z), 1233yd(E) and water isobtained through the production method. The reaction compositionobtained through the method may be used as the distillation compositionas it is, or a composition which is prepared by adding at least one kindselected from 1233yd(E) and water in accordance with the contents ofwater and 1233yd(E) contained in the reaction composition may be used asthe distillation composition.

The reaction composition can be classified as described below. That is,the classification can be made into a reaction composition (firstreaction composition) which contains 1233yd(Z) and water, and does notcontain 1233yd(E), a reaction composition (second reaction composition)which contains 1233yd(Z) and 1233yd(E), and does not contain water, anda reaction composition (third reaction composition) which contains1233yd(Z), 1233yd(E) and water.

In a case of the first reaction composition, that is, 1233yd(Z) andwater are contained and 1233yd(E) is not contained, the distillationcomposition can be obtained by adding 1233yd(E). The azeotropiccomposition or the azeotropic-like composition of 1233yd(E) and watercan be formed by adding 1233yd(E).

In a case of the second reaction composition, that is, 1233yd(Z) and1233yd(E) are contained and water is not contained, the distillationcomposition can be obtained by adding water. The azeotropic compositionor the azeotropic-like composition of 1233yd(E) and water can be formedby adding water.

In a case of the third reaction composition, that is, 1233yd(Z), waterand 1233yd(E) are contained, it can be used as the distillationcomposition as it is. Note that at least one kind selected from1233yd(E) and water can be added to the third reaction composition inaccordance with the contents of water and 1233yd(E).

A content of 1233yd(Z) in the distillation composition used in thisembodiment is preferably 50 mass % or more with respect to a totalamount of the distillation composition, more preferably 80 mass % ormore, and further preferably 90 mass % or more. It is possible toefficiently remove 1233yd(E) and water if the content of 1233yd(Z) isthe above-stated lower limit value or more.

Respective contents of water and 1233yd(E) in the distillationcomposition are not necessarily limited. The azeotropic composition orthe azeotropic-like composition can be formed from water and 1233yd(E)owing to the water and 1233yd(E) contained in the distillationcomposition.

It is preferable that all of 1233yd(E) and water contained in thedistillation composition are efficiently removed from the distillationcomposition by forming the azeotropic composition or the azeotropic-likecomposition. In this context, the content ratio of water with respect toa sum total of the content of 1233yd(E) and the content of water ispreferably 0.001 to 5 mass %, more preferably 0.01 to 2.5 mass %,further preferably 0.05 to 2 mass %, and particularly preferably 0.1 to2 mass % in the distillation composition.

The ratio of water can be adjusted by adding 1233yd(E) or water. Forexample, when the ratio of water is small, the ratio of water can beincreased by adding water. When the ratio of water is large, the ratioof water can be decreased by adding 1233yd(E).

The distillation composition may contain components other than1233yd(Z), 1233yd(E) and water. Examples of the components other than1233yd(Z), 1233yd(E) and water include a production raw material of1233yd(Z), by-products generated in addition to 1233yd(Z) and 1233yd(E),and the like. Concretely, the examples of the components other than1233yd(Z), 1233yd(E) and water include HCFC-244ca,1-chloro-3,3-difluoro-1-propyne, 1,1,2,2,3-pentafluoropropane,2,3,3-trifluoro-1-propene, 1,2,3,3-tetrafluoro-1-propene, alcohol suchas tetrafluoropropanol and methanol, and the like. The components otherthan 1233yd(Z), 1233yd(E) and water are preferably 30 mass % or less,and more preferably 10 mass % or less with respect to a total amount ofthe distillation composition in terms of increasing the recovery ratioof 1233yd(Z). In particular, since alcohol such as tetrafluoropropanoland methanol has a possibility of obstructing the formation of theazeotropic component of 1233yd(E) and water, a compound of these ispreferably 5 mass % or less, and more preferably 1 mass % or less withrespect to the total amount of the distillation composition when thecompound is contained.

Next, distillation is explained.

In the method for producing 1233yd(Z) of this embodiment, distillationis carried out by using the distillation composition containing1233yd(Z), 1233yd(E) and water. It is possible to form the azeotropiccomposition or the azeotropic-like composition of 1233yd(E) and water bymaking 1233yd(E) and water coexist in the distillation composition.

Since the boiling point of the azeotropic composition or theazeotropic-like composition of 1233yd(E) and water is about 40 to 48° C.where the boiling point of 1233yd(Z) is about 54° C., it is possible toremove at least a part of the azeotropic composition or theazeotropic-like composition of 1233yd(E) and water from the distillationcomposition by distilling the distillation composition. As a result, acomposition where the contents of 1233ye(E) and water are reduced, thatis, 1233yd(Z) with high purity can be obtained.

A publicly-known distillation apparatus can be used as a distillationapparatus as long as it is possible to remove at least a part of theazeotropic composition or the azeotropic-like composition of 1233yd(E)and water from the distillation composition.

FIG. 1 illustrates an example of the distillation apparatus.

A distillation apparatus 10 includes, for example, a distillation column11, where a pipe 12 supplying the distillation composition, a pipe 13taking out a distillate from a column top of the distillation column 11,and a pipe 14 taking out a bottom product from a column bottom of thedistillation column 11 are connected to the distillation column 11. Thedistillation apparatus 10 may be either a batch type or a continuoustype. The distillation column 11 may be either a hollow type or amultiplate type.

In the distillation apparatus 10 as stated above, for example, adistillate containing the azeotropic composition or the azeotropic-likecomposition of 1233yd(E) and water can be obtained from the column top,and a bottom product containing 1233yd(Z) can be obtained from thecolumn bottom.

When excessive 1233yd(E) or water which exceeds the composition range ofthe azeotropic composition or the azeotropic-like composition of1233yd(E) and water is contained in the distillation composition, theexcessive 1233yd(E) or water may be contained in, for example, thebottom product from the column bottom.

In a case of the multiplate distillation column 10, the distillationcomposition is generally supplied to a middle plate of the multiplatedistillation column 10. In this case, the distillate containing theazeotropic composition or the azeotropic-like composition of 1233yd(E)and water can be obtained from upper-side plates than the plate wherethe distillation composition is supplied. The bottom product containing1233yd(Z) can be obtained from lower-side plates than the plate wherethe distillation composition is supplied.

A pressure at the distillation time is preferably 0.1 to 1.0 MPa inabsolute pressure. When the pressure is set in the range, a column toptemperature of the distillation column is preferably 40 to 80° C. Bysetting the pressure at the distillation time and the column toptemperature of the distillation column in the above-stated ranges, atleast a part of the azeotropic composition or the azeotropic-likecomposition of 1233yd(E) and water can be efficiently removed from thedistillation composition.

For example, when the pressure at the distillation time is 0.1 MPa inabsolute pressure, the column top temperature of the distillation columnis preferably 40° C. or more, more preferably 43° C. or more, andfurther preferably 45° C. or more in terms of increasing a recoveryamount of the distillate containing the azeotropic composition or theazeotropic-like composition of 1233yd(E) and water. The column toptemperature is preferably 55° C. or less, more preferably 52° C. orless, further preferably 50° C. or less, and the most preferably 48° C.or less in terms of decreasing a ratio of 1233yd(Z) contained in thedistillate.

It is possible to carry out the distillation again while using thebottom product containing 1233yd(Z) as the distillation composition.When 1233yd(E) and water are contained in the bottom product, 1233yd(E)and water can be separated by carrying out the distillation, and thebottom product where the purity of 1233yd(Z) is further increased can beobtained.

The distillate where the ratio of 1233yd(E) and water is increased canbe obtained by carrying out the distillation again while using thedistillate containing 1233yd(E) as the distillation composition.Besides, 1233yd(E) with high purity can be obtained by dehydrating theobtained distillate through a later-described method or the like.

According to the method for producing 1233yd(Z) of this embodiment, arecovery ratio of the bottom product can be set to, for example, 83% ormore by carrying out the distillation. The recovery ratio of the bottomproduct is preferably 84% or more, and more preferably 85% or more.Here, the recovery ratio of the bottom product [%] is calculated by thefollowing expression from a supply amount of the distillationcomposition and a recovery amount of the bottom product.

Recover ratio of bottom product [%]==(recovery amount of bottomproduct)/(supply amount of distillation composition)×100

According to the method for producing 1233yd(Z) of this embodiment, therecovery ratio of 1233yd(Z) in the bottom product can be set to, forexample, 85% or more by carrying out the distillation. The recoveryratio of 1233yd(Z) in the bottom product is preferably 90% or more, andmore preferably 95% or more. Here, the recovery ratio of 1233yd(Z) inthe bottom product [%] is calculated by the following expression from asupply amount of 1233yd(Z) in the distillation composition and arecovery amount of 1233yd(Z) in the bottom product.

Recovery ratio of 1233yd(Z) in bottom product [%]=(recovery amount of1233yd(Z) in bottom product)/(supply amount of 1233yd(Z) in distillationcomposition)×100

According to such distillation, it is possible to set a content ratio of1233yd(Z) (purity of 1233yd(Z)) with respect to a sum total of contentsof 1233yd(Z), 1233yd(E) and water in the bottom product to be, forexample, 80 mass % or more. The ratio is preferably 90 mass % or more,more preferably 93 mass % or more, further preferably 95 mass % or more,and the most preferably 98 mass % or more.

By bringing the bottom product obtained by the distillation into contactwith a solid absorbent, the content of water in the bottom product canbe decreased. An example of the solid absorbent includes, for example,silica. Silica is a substance mainly having a chemical composition ofSiO₂. Examples of silica include porous synthetic silica gel, mesoporoussilica, silica alumina, and the like. One kind of silica may be usedindependently, or two or more kinds may be used together. A form ofsilica is not particularly limited, and may be a powder form, afine-particle form, a granular form, a thin-film form, and the like.

EXAMPLES

Hereinafter, the present invention is explained in detail by way ofexamples. It should be noted that the present invention is not limitedby these examples.

Example 1

A multiplate distillation column having a theoretical plate number of 50was prepared as the distillation column. The distillation compositionwas supplied with a supply amount of 1.0 kg/h from a part of a 40thplate from the column top of the distillation column. As listed in Table1, 0.8800 kg/h of 1233yd(Z), 0.0050 kg/h of water, and 0.1150 kg/h of1233yd(E) were supplied as the distillation composition. After that, anoperating pressure was set to the atmospheric pressure, the column toptemperature was set to 45.5° C. and continuous distillation was carriedout.

During the distillation, a distillate was pulled out from a column top,and a bottom product was pulled out from a column bottom. A recoveryamount of water was found by using the Karl Fischer moisture meter, andrecovery amounts of 1233yd(Z) and 1233yd(E) were found by using gaschromatography regarding the distillate and the bottom product. Besides,a recovery ratio (recovery amount/supply amount) was calculated from thesupply amount and the recovery amount.

Supply amounts of the distillation composition are listed and recoveryamounts and recovery ratios of the distillate and the bottom product arerespectively listed in Table 1. Compositions of the distillationcomposition, the distillate, and the bottom product and a ratio of waterin 1233yd(E) and water are listed in Table 2.

The composition of the distillation composition can be found from thesupply amount of each component. The compositions of the distillate andthe bottom product can be found from the recovery amount of eachcomponent. The ratio of water in 1233yd(E) and water can be found fromthe supply amount or the recovery amount of 1233yd(E) and water.

TABLE 1 Distillation composition Distillate Bottom product SupplyRecovery Recovery amount amount Recovery amount Recovery [kg/h] [kg/h]ratio [%] [kg/h] ratio [%] 1233yd(Z) 0.8800 0.0300 3.4 0.8500 96.6 Water0.0050 0.0049 98.0 0.0001 2.0 1233yd(E) 0.1150 0.1110 96.5 0.0040 3.5Total 1.0000 0.1459 14.6 0.8541 85.4

TABLE 2 Distillation composition Distillate Bottom product Composition1233yd(Z) 88.00 20.56 99.52 [mass %] Water 0.50 3.36 0.01 1233yd(E)11.50 76.08 0.47 Ratio of water [mass %] *1 4.17 4.23 2.44 *1: A contentratio of water with respect to a sum total of a content of 1233yd(E) anda content of water.

As it is clear from Tables 1, 2, the recovery ratio of the bottomproduct can be set to 83 mass % or more, and a content ratio of1233yd(Z) in the bottom product can be set to 85 mass % or more by usingthe distillation composition containing 1233yd(Z), 1233yd(E) and water.

Example 2

As listed in Table 3, distillation and measurement were carried out assame as Example 1 except that the supply amount of each component in thedistillation composition was changed and the column top temperature wasset to 47.5° C. Recovery amounts and recovers ratios of the distillateand the bottom product are respectively listed in Table 3. Thecompositions of the distillation composition, the distillate, and thebottom product, and the ratio of water in 1233yd(E) and water arerespectively listed in Table 4.

TABLE 3 Distillation composition Distillate Bottom product SupplyRecovery Recovery amount amount Recovery amount Recovery [kg/h] [kg/h]ratio [%] [kg/h] ratio [%] 1233yd(Z) 0.8800 0.0300 3.4 0.8500 96.6 Water0.0005 0.0005 100.0 0.0000 0.0 1233yd(E) 0.1195 0.1170 97.9 0.0025 2.1Total 1.0000 0.1475 14.7 0.8525 85.3

TABLE 4 Distillation composition  Distillate Bottom product Composition1233yd(Z) 88.00 20.34 99.71 [mass %] Water 0.05 0.33 0.00  1233yd(E)11.95 79.33 0.29 Ratio of water [mass %] *1 0.42 0.42 0.00 *1: A contentratio of water with respect to a sum total of a content of 1233yd(E) anda content of water.

As it is clear from Tables 3, 4, the recovery ratio of the bottomproduct can be set to 83 mass % or more, and the content ratio of1233yd(Z) in the bottom product can be set to 85 mass % or more by usingthe distillation composition containing 1233yd(Z), 1233yd(E) and water.

Example 3

As listed in Table 5, distillation and measurement were carried out assame as Example 1 except that the supply amount of each component in thedistillation composition was changed and the column top temperature wasset to 51.5° C. Recovery amounts and recovers ratios of the distillateand the bottom product are respectively listed in Table 5. Thecompositions of the distillation composition, the distillate, and thebottom product, and the ratio of w ater in 1233yd(E) and water arerespectively listed in Table 6.

TABLE 5 Distillation composition Distillate Bottom product SupplyRecovery Recovery amount amount Recovery amount Recovery [kg/h] [kg/h]ratio [%] [kg/h] ratio [%] 1233yd(Z) 0.9850 0.1350 13.7 0.8500 86.3Water 0.0050 0.0049 98.0 0.0001 2.0 1233yd(E) 0.0100 0.0100 100.0 0.00000.0 Total 1.0000 0.1499 15.0 0.8501 85.0

TABLE 6 Distillation composition Distillate Bottom product Composition1233yd(Z) 98.50 90.06 99.99 [mass %] Water 0.50 3.27 0.01 1233yd(E) 1.006.67 0.00 Ratio of water [mass %] *1 33.33 32.89 100.00 *1: A contentratio of water with respect to a sum total of a content of 1233yd(E) anda content of water.

As it is clear from Tables 5, 6, the recovery ratio of the bottomproduct can be set to 83 mass % or more, and the content ratio of1233yd(Z) in the bottom product can be set to 85 mass % or more by usingthe distillation composition containing 1233yd(Z), 1233yd(E) and water.

Example 4

As listed in Table 7, distillation and measurement were carried out assame as Example 1 except that the supply amount of each component in thedistillation composition was changed. The distillation composition usedin Example 4 was obtained by bringing1-chloro-2,2,3,3-tetrafluoropropane into contact with aqueous potassiumhydroxide solution at 50° C. to cause a dehydrofluorination reaction. Asa result of analyzation of a crude liquid after the dehydrofluorinationreaction, there were contained unreacted HCFC-244ca,1-chloro-3,3-difluoropropyne where 1233yd was further subjected to thedehydrofluorination reaction, a compound represented by a molecularformula CHCl=C(CHF₂)OCH₂CF₂CHF₂ where tetrafluoropropanol (TFPO) wasadded to 1233yd and the dehydrofluorination reaction was further carriedout or TFPO was added to 1-chloro-3,3-difluoropropyne (hereinafter, itis denoted by 1233yd-TFPO adduct) as by-products in addition to1233yd(Z), 1233yd(E).

Recovery amounts and recovery ratios of the distillate and the bottomproduct are respectively listed in Table 7. The compositions of thedistillation composition, the distillate, and the bottom product, andthe ratio of water in 1233yd(E) and water are respectively listed inTable 8.

TABLE 7 Distillation composition Distillate Bottom product SupplyRecovery Recovery amount amount Recovery amount Recovery [kg/h] [kg/h]ratio [%] [kg/h] ratio [%] 1233yd(Z) 0.7970 0.0167 2.1 0.7802 97.90Water 0.0060 0.0059 98.3 0.0001 1.70 1233yd(E) 0.0778 0.0745 95.8 0.00334.20 244ca 0.0596 0.0332 55.6 0.0265 44.40 1-chloro- 0.0398 0.0390 98.10.0008 1.90 3,3- difluoro- propyne 1233yd- 0.0199 0.0001 0.5 0.019899.50 TFPO adducts Total 1.0000 0.1694 16.9 0.8306 83.1

TABLE 8 Distillation Bottom composition Distillate product Composition1233yd(Z) 79.90 9.88 93.93 [mass %] Water 0.60 3.48 0.01 1233yd(E) 7.7843.98 0.39 244ca 5.96 19.57 3.19 1-chloro- 3.98 23.03 0.093,3-difluoropropyne Water 1.99 0.06 2.38 Ratio of water [mass %] *1 7.167.33 2.50 *1: A content ratio of water with respect to a sum total of acontent of 1233yd(E) and a content of water.

As it is clear from Tables 7, 8, the recovery ratio of the bottomproduct can be set to 83 mass % or more, and the content ratio of1233yd(Z) in the bottom product can be set to 85 mass % or more by usinga reaction composition obtained by subjecting1-chloro-2,2,3,3-tetrafluoropropane to the defluorination reaction asthe distillation composition.

Comparative Example 1

As listed in Table 9, distillation and measurement were carried out assame as Example 1 except that the supply amount of each component in thedistillation composition was changed and the column top temperature wasset to 53.0° C. Recovery amounts and recovery ratios of the distillateand the bottom product are respectively listed in Table 9. Thecompositions of the distillation composition, the distillate, and thebottom product, and the ratio of water in 1233yd(E) and water arerespectively listed in Table 10.

TABLE 9 Distillation composition Distillate Bottom product SupplyRecovery Recovery amount amount Recovery amount Recovery [kg/h] [kg/h]ratio [%] [kg/h] ratio [%] 1233yd(Z) 0.9950 0.1870 18.8 0.8080 81.2Water 0.0050 0.0047 94.0 0.0003  6.0 1233yd(E) — — — — — Total 1.00000.1917 19.2 0.8083 80.8

TABLE 10 Distillation composition Distillate Bottom product Composition 1233yd(Z) 99.50 97.55 99.96 [mass %] Water 0.50 2.45 0.04 1233yd(E)0.00 0.00 0.00 Ratio of water [mass %] *1 100.00 100.00 100.00 *1: Acontent ratio of water with respect to a sum total of a content of1233yd(E) and a content of water.

As it is clear from Tables 9, 10, the distillation composition ofComparative Example 1 contains 1233yd(Z) and water, and does not contain1233yd(E). When 1233yd(E) is not contained, the recovery ratio of thebottom product decreases compared to the case when 1233yd(E) iscontained. Further, it can be seen that 1233yd(Z) and water are notsufficiently separated.

According to the present invention, 1233yd(E) and water can beefficiently removed, a recovery ratio of 1233yd(Z) can be increased, andpurity of 1233yd(Z) can be increased. Accordingly, it can be effectivelyused for various fields such as a cleaning agent, a solvent, and arefrigerant where 1233yd(Z) is used.

1-6. (canceled) 7: A composition, comprising:(Z)-1-chloro-2,3,3-trifluoro-1-propene;(E)-1-chloro-2,3,3-trifluoro-1-propene; and water, wherein a proportionof (Z)-1-chloro-2,3,3-trifluoro-1-propene with respect to a sum total ofcontents of the (Z)-1-chloro-2,3,3-trifluoro-1-propene,(E)-1-chloro-2,3,3-trifluoro-1-propene and water is 90 mass % or more.8: The composition according to claim 7, wherein a content of water inthe composition is 0.01% or less. 9: The composition according to claim7, wherein the proportion of (Z)-1-chloro-2,3,3-trifluoro-1-propene withrespect to a sum total of contents of the(Z)-1-chloro-2,3,3-trifluoro-1-propene,(E)-1-chloro-2,3,3-trifluoro-1-propene and water is 93 mass % or more.10: The composition according to claim 7, wherein the proportion of(Z)-1-chloro-2,3,3-trifluoro-1-propene with respect to a sum total ofcontents of the (Z)-1-chloro-2,3,3-trifluoro-1-propene,(E)-1-chloro-2,3,3-trifluoro-1-propene and water is 95 mass % or more.11: The composition according to claim 7, wherein the proportion of(Z)-1-chloro-2,3,3-trifluoro-1-propene with respect to a sum total ofcontents of the (Z)-1-chloro-2,3,3-trifluoro-1-propene,(E)-1-chloro-2,3,3-trifluoro-1-propene and water is 98 mass % or more.